The phrase originates from military contexts where high standards of appearance are expected. The new cadet learned quickly that spit and polish was vital to impress his superiors.
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Metaphoric Use
Often used metaphorically to describe any effort to perfect something, not just cleaning. Her presentation had the spit and polish of a seasoned professional.
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Not Literal Spit
Originally, spit might have been used for polishing, but now it's about the effort, not saliva. The term 'spit and polish' doesn't mean he actually used spit to clean his trumpet.